skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Modeling solubility of CO 2 gas in room temperature ionic liquids using the COSMOSAC-LANL model: a first principles study

Abstract

In this paper we present a thermodynamic model for asymmetric solutions with a special emphasis on solute–solvent interactions. The new “COSMOSAC-LANL” activity coefficient model is rooted in first principles calculations based on the COSMO model where the microscopic information passes to the macroscopic world via a dielectric continuum solvation model followed by a post statistical thermodynamic treatment of self-consistent properties of the solute particle. To model the activity coefficient at infinite dilution for the binary mixtures, a 3-suffix Margules (3sM) function is introduced to model asymmetric interactions and, for the combinatorial term, the Staverman–Guggenheim (SG) form is used. The new “COSMOSAC-LANL” activity coefficient model has been used to calculate the solubility of CO 2 in room temperature ionic liquids and to model the selectivity between CO 2 and CH 4 gases. We have shown improved solubility and selectivity prediction of CO 2 and CH 4 gas in room temperature ionic liquids using the ADF-COSMOSAC-2013 model with the new “LANL” activity coefficient model. The calculated values have been compared with experimental results where they are available.

Authors:
ORCiD logo [1];  [2]
  1. Theoretical Division (T-1), Los Alamos National Laboratory, Los Alamos 87545, USA
  2. MPA-11 Division, Los Alamos National Laboratory, Los Alamos 87545, USA
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1561377
Alternate Identifier(s):
OSTI ID: 1570644
Report Number(s):
LA-UR-19-22863
Journal ID: ISSN 1463-9076; PPCPFQ
Grant/Contract Number:  
20170046DR; 89233218CNA000001
Resource Type:
Journal Article: Published Article
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print) Journal Volume: 21 Journal Issue: 35; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; CO2 gas capture; Ionic Liquids; COSMOSAC

Citation Formats

Karmakar, Anwesa, and Mukundan, Rangachary. Modeling solubility of CO 2 gas in room temperature ionic liquids using the COSMOSAC-LANL model: a first principles study. United Kingdom: N. p., 2019. Web. doi:10.1039/C9CP02725D.
Karmakar, Anwesa, & Mukundan, Rangachary. Modeling solubility of CO 2 gas in room temperature ionic liquids using the COSMOSAC-LANL model: a first principles study. United Kingdom. doi:10.1039/C9CP02725D.
Karmakar, Anwesa, and Mukundan, Rangachary. Wed . "Modeling solubility of CO 2 gas in room temperature ionic liquids using the COSMOSAC-LANL model: a first principles study". United Kingdom. doi:10.1039/C9CP02725D.
@article{osti_1561377,
title = {Modeling solubility of CO 2 gas in room temperature ionic liquids using the COSMOSAC-LANL model: a first principles study},
author = {Karmakar, Anwesa and Mukundan, Rangachary},
abstractNote = {In this paper we present a thermodynamic model for asymmetric solutions with a special emphasis on solute–solvent interactions. The new “COSMOSAC-LANL” activity coefficient model is rooted in first principles calculations based on the COSMO model where the microscopic information passes to the macroscopic world via a dielectric continuum solvation model followed by a post statistical thermodynamic treatment of self-consistent properties of the solute particle. To model the activity coefficient at infinite dilution for the binary mixtures, a 3-suffix Margules (3sM) function is introduced to model asymmetric interactions and, for the combinatorial term, the Staverman–Guggenheim (SG) form is used. The new “COSMOSAC-LANL” activity coefficient model has been used to calculate the solubility of CO2 in room temperature ionic liquids and to model the selectivity between CO2 and CH4 gases. We have shown improved solubility and selectivity prediction of CO2 and CH4 gas in room temperature ionic liquids using the ADF-COSMOSAC-2013 model with the new “LANL” activity coefficient model. The calculated values have been compared with experimental results where they are available.},
doi = {10.1039/C9CP02725D},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
issn = {1463-9076},
number = 35,
volume = 21,
place = {United Kingdom},
year = {2019},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1039/C9CP02725D

Figures / Tables:

Fig. 1 Fig. 1: A cartoon representation of asymmetric interaction in a binary mixture at infinite dilution.

Save / Share:

Works referenced in this record:

ILThermo:  A Free-Access Web Database for Thermodynamic Properties of Ionic Liquids
journal, July 2007

  • Dong, Qian; Muzny, Chris D.; Kazakov, Andrei
  • Journal of Chemical & Engineering Data, Vol. 52, Issue 4
  • DOI: 10.1021/je700171f

Solubility of Tetrafluoromethane in the Ionic Liquid [hmim][Tf 2 N]
journal, March 2008

  • Kumełan, Jacek; Pérez-Salado Kamps, Álvaro; Tuma, Dirk
  • The Journal of Physical Chemistry B, Vol. 112, Issue 10
  • DOI: 10.1021/jp076737t

Screening of ionic liquids for CO2 capture using the COSMO-SAC model
journal, January 2015


Molecular Origins of the Apparent Ideal CO 2 Solubilities in Binary Ionic Liquid Mixtures
journal, September 2018

  • Kapoor, Utkarsh; Shah, Jindal K.
  • The Journal of Physical Chemistry B, Vol. 122, Issue 42
  • DOI: 10.1021/acs.jpcb.8b08223

Ionic liquids as amphiphile self-assembly media
journal, January 2008

  • Greaves, Tamar L.; Drummond, Calum J.
  • Chemical Society Reviews, Vol. 37, Issue 8
  • DOI: 10.1039/b801395k

COSMOSPACE: Alternative to conventional activity-coefficient models
journal, October 2002

  • Klamt, Andreas; Krooshof, Gerard J. P.; Taylor, Ross
  • AIChE Journal, Vol. 48, Issue 10
  • DOI: 10.1002/aic.690481023

Solubility model of metal complex in ionic liquids from first principle calculations
journal, January 2019

  • Karmakar, Anwesa; Mukundan, Rangachary; Yang, Ping
  • RSC Advances, Vol. 9, Issue 32
  • DOI: 10.1039/C9RA04042K

Improvements of COSMO-SAC for vapor–liquid and liquid–liquid equilibrium predictions
journal, October 2010


Statistical thermodynamic model for viscosity of pure liquids and liquid mixtures
journal, November 1992

  • Cao, Weihong; Fredenslund, Aage; Rasmussen, Peter
  • Industrial & Engineering Chemistry Research, Vol. 31, Issue 11
  • DOI: 10.1021/ie00011a027

Refinement and Parametrization of COSMO-RS
journal, June 1998

  • Klamt, Andreas; Jonas, Volker; Bürger, Thorsten
  • The Journal of Physical Chemistry A, Vol. 102, Issue 26
  • DOI: 10.1021/jp980017s

Local compositions in thermodynamic excess functions for liquid mixtures
journal, January 1968


Modeling of the Carbon Dioxide Solubility in Imidazolium-Based Ionic Liquids with the tPC-PSAFT Equation of State
journal, May 2006

  • Kroon, Maaike C.; Karakatsani, Eirini K.; Economou, Ioannis G.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 18
  • DOI: 10.1021/jp060300o

Gibbs-duhem-margules laws
journal, January 1996


What Determines CO 2 Solubility in Ionic Liquids? A Molecular Simulation Study
journal, July 2015

  • Klähn, Marco; Seduraman, Abirami
  • The Journal of Physical Chemistry B, Vol. 119, Issue 31
  • DOI: 10.1021/acs.jpcb.5b03674

An Improvement to COSMO-SAC for Predicting Thermodynamic Properties
journal, April 2014

  • Xiong, Ruichang; Sandler, Stanley I.; Burnett, Russell I.
  • Industrial & Engineering Chemistry Research, Vol. 53, Issue 19
  • DOI: 10.1021/ie404410v

State-of-the-Art of CO 2 Capture with Ionic Liquids
journal, June 2012

  • Ramdin, Mahinder; de Loos, Theo W.; Vlugt, Thijs J. H.
  • Industrial & Engineering Chemistry Research, Vol. 51, Issue 24
  • DOI: 10.1021/ie3003705

Modeling the Solubility Behavior of CO 2 , H 2 , and Xe in [C n -mim][Tf 2 N] Ionic Liquids
journal, December 2008

  • Andreu, Jordi S.; Vega, Lourdes F.
  • The Journal of Physical Chemistry B, Vol. 112, Issue 48
  • DOI: 10.1021/jp807484g

Solvation quantities from a COSMO-RS equation of state
journal, November 2015

  • Panayiotou, C.; Tsivintzelis, I.; Aslanidou, D.
  • The Journal of Chemical Thermodynamics, Vol. 90
  • DOI: 10.1016/j.jct.2015.07.011

COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient
journal, January 1993


Thermodynamic description of the solvophobic effect in ionic liquids
journal, October 2016


Equation of state modeling of the phase equilibria of ionic liquid mixtures at low and high pressure
journal, January 2008

  • Karakatsani, Eirini K.; Economou, Ioannis G.; Kroon, Maaike C.
  • Physical Chemistry Chemical Physics, Vol. 10, Issue 40
  • DOI: 10.1039/b806584p

Enthalpic Driving Force for the Selective Absorption of CO 2 by an Ionic Liquid
journal, February 2018

  • Daly, Clyde A.; Brinzer, Thomas; Allison, Cecelia
  • The Journal of Physical Chemistry Letters, Vol. 9, Issue 6
  • DOI: 10.1021/acs.jpclett.8b00347

On the origin of ionicity in ionic liquids. Ion pairing versus charge transfer
journal, January 2014

  • Hollóczki, Oldamur; Malberg, Friedrich; Welton, Tom
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 32
  • DOI: 10.1039/C4CP01177E

Capturing the Solubility Behavior of CO 2 in Ionic Liquids by a Simple Model
journal, November 2007

  • Andreu, Jordi S.; Vega, Lourdes F.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 43
  • DOI: 10.1021/jp074353x

A Priori Phase Equilibrium Prediction from a Segment Contribution Solvation Model
journal, March 2002

  • Lin, Shiang-Tai; Sandler, Stanley I.
  • Industrial & Engineering Chemistry Research, Vol. 41, Issue 5
  • DOI: 10.1021/ie001047w

Simultaneous correlation of viscosity and vapor-liquid equilibrium data
journal, September 1993

  • Cao, Weihong; Knudsen, Kim; Fredenslund, Aage
  • Industrial & Engineering Chemistry Research, Vol. 32, Issue 9
  • DOI: 10.1021/ie00021a033

Group-contribution estimation of activity coefficients in nonideal liquid mixtures
journal, November 1975

  • Fredenslund, Aage; Jones, Russell L.; Prausnitz, John M.
  • AIChE Journal, Vol. 21, Issue 6
  • DOI: 10.1002/aic.690210607

Liquid—liquid phase splitting—I analytical models for critical mixing and azeotropy
journal, January 1983


Correlation of infinite dilution activity coefficient of solute in ionic liquid using UNIFAC model
journal, March 2008


The entropy of high polymer solutions. Generalization of formulae
journal, January 1950


COSMO-RS: a novel and efficient method for the a priori prediction of thermophysical data of liquids
journal, July 2000